JPH01291238A - Silver halide photographic emulsion - Google Patents

Abstract

PURPOSE:To obtain a joint type silver halide particle with reduced latent image dispersion and high illumination sensitivity by incorporating >=30% of joint particles having one jointing part per a particle, respectively based on the total particles in the title emulsion. CONSTITUTION:The particles having >=30% of projecting area of the total silver halide particles are composed of the joint type silver halide particle, and the joint particle has substantially one of jointing part per one of the particle. Namely, the joint particle has substantially one one of epitaxial growth part V1 per a substrate particle. And, the crystal structure of the substrate particle is constituted of a rock salt structure. Thus, the photographic emulsion with the reduced latent image dispersion and the sufficiently high illumination sensitivity is obtd.

Description

Detailed Description of the Invention (Technical Field of the Invention) The present invention relates to a silver halide photographic emulsion and a photographic light-sensitive material using the same, and particularly to silver halide grains having a novel morphology and a method for producing the same. It is something.

(Prior Art and Its Disadvantages) In recent years, as films have become smaller in format and photographing conditions have become more diverse, there has been a strong demand for films that have increasingly high sensitivity and a wide range of exposure suitability. Under these circumstances, the basic performance of the silver halide in the emulsion is increasingly required to be high sensitivity, low fog, and fine grain. These improvements in performance contribute to the advancement of silver halide photosensitive materials as a whole. In order to create emulsions with high sensitivity and fine grains, it is desirable to reduce inefficiency in the sensitization process and increase the inherent quantum sensitivity of the grains. Possible inefficiency factors related to this quantum sensitivity include recombination, latent image dispersion, and competitive electron traps originating from structural defects.

There is a lot of conventional knowledge regarding hybrid silver halide crystals, which are formed by epitaxially bonding crystals with different halogen compositions to specific parts of the grains of a substrate in the formation of silver halide grains. For example, JP-A-53-10372
In step 5, silver chloride crystals are grown epitaxially on a silver iodide crystal substrate whose light absorption extends to long wavelengths, producing particles with the spectral sensitivity of silver iodide and the developability of silver chloride, improving photographic sensitivity. Examples are disclosed. Japanese Patent Publication No. 59-133540
The issue mainly includes (1111
A method for producing particles with high sensitivity is disclosed by epitaxially growing a silver salt at a selected site in the presence of a site-indicating agent on a host particle surrounded by crystal planes.

In the bonded particles described therein, the bond is limited to a face, a ridge, a vertex, or a combination thereof within one particle using a site-indicating agent. Therefore, as shown in FIG. 3 of JP-A No. 59-133540, even when the bonding portions are limited to the vertices, each particle has substantially six or more bonding portions. In the case of in-plane epitaxial growth (as shown in FIG. 5), the junction extends over the entire grain surface and can no longer be counted as a junction.

JP-A No. 53-103725 describes an example in which silver chloride was grown epitaxially using a β-phase silver iodide crystal with a wurtzite crystal structure as a substrate. It is stated that generally there is one location per particle. However, in the case of substrate grains consisting of silver bromide, silver chloride, silver iodobromide, silver bromochloride, and silver chloroiodobromide crystals having a rock salt structure, bonded grains in which the bonding portion is limited to one location, JP-A-53-103
There is no example of this in any other published literature, let alone in No. 72.5.

JP-A-59-133540 describes that silver salt epitaxy has a function as an electron trap during the latent image formation process. When considering latent image dispersion as an inefficiency factor regarding quantum sensitivity, the bonded particles that have been disclosed so far, which have multiple or large-area bonding parts, tend to cause latent image dispersion and have insufficient high-light sensitivity. It was something.

(Objective of the Invention) An object of the present invention is to provide a silver halide emulsion with reduced latent image dispersion and high sensitivity to high illuminance.

In particular, it is an object of the present invention to provide a photographic emulsion comprising bonded silver halide grains with reduced latent image dispersion and high sensitivity to high illuminance.

(Disclosure of the Invention) An object of the present invention is to provide a silver halide photographic emulsion comprising silver halide grains dispersed in a binder, in which 30% or more of the projected area of all silver halide grains are bonded halogenated. A silver halide photographic emulsion comprising silver particles, each bonded particle having substantially one bonding part per particle, and a substrate grain having a crystal structure of a rock salt structure, and a silver halide photographic emulsion comprising the same. This was achieved by the photosensitive material used.

Bonded particles (hereinafter referred to as (one-point inspection type particles)) having substantially one bonding site per particle of the present invention are defined as follows.

As shown in FIG. 1, (a) and (b) in which there is essentially only one epitaxial growth region with respect to the substrate grain are (
Even when the total volume of the micro-growth areas (■2) is smaller than 20% of the volume of the main growth areas (■,) as in C), this is also considered a one-point inspection type particle.

(Summary of the Invention) The present inventors added silver and λ halogen again after adding a spectral sensitizing dye or adsorbent photographic additive of 100% or more of the saturated coverage of the silver halide crystal serving as the substrate. Alternatively, by adding fine grains and performing physical ripening, a silver salt is epitaxially grown to produce a silver halide emulsion in which the number of bonded grains having substantially one bonding site per grain accounts for 30% or more of the total number of grains. I found out what I can get.

At this time, the amount of the spectral sensitizing dye or adsorbent additive to be added must be at least 100% of the saturated adsorption amount of the substrate emulsion, preferably at least 150%, and more preferably at least 180%. It is.

Further, it is important that the substrate particles contain iodine, and in particular, when the amount of the dye added is less than 150% of the saturated adsorption amount, it is preferable that the substrate particles contain iodine in an amount of 3 mol % or more.

Dyes for use in the present invention include polymethine dyes including cyanine, merocyanine, complex cyanine and complex merocyanine (i.e. tritetra-2 and polynuclear cyanine and merocyanine), oxole, hemioxonol, styryl, merostyryl and streptocyanine. is included.

Cyanine spectral sensitizing dyes include quinolinium, pyridinium, isoquinolinium, 3H-indolium, benz(
e) Indolium, oxazolium, oxazolinium, thiazolium, thiazolinium, selenazolium, selenacylinium, imidazolium, imidazolinium,
Penzukizazolinium, benzothiazolium, benzoselenazolium, penzimidazolium, naphthoxazolium, naphthothiazolium, naphthoselenazolium, thiazolinium, dihydronaphthothiazolium, sodium and imidazopyrazinium It includes two basic heterocyclic nuclei joined by a methine linkage, as derived from a quaternary salt.

Merocyanine spectral sensitizing dyes include barbituric acid, 2-
Thiobarbic acid, rhodanine, hydantoin, 2-
Thiohydantoin, 4-thiohydantoin, 2-pyrazolin-5-one, 2-isoxazolin-5-one, indan-1,3-dione, cyclohexane-1,3-dione, 1,3-dioxane-4,6- Acidic nuclei and cyanine dye types such as those derived from Zion, pyrazoline-3°5-dione, pentane-2,4-dione, argylsulfonylacetonitrile, malononitrile, isoquinolin-4-one and chroman-2,4-dione. and a basic heterocyclic nucleus linked through a methine bond. Various supersensitization techniques can be used for color sensitization in the present invention. Examples of useful dye combinations, including supersensitizing dye combinations, include U.S. Pat.
No. 672.898. An example of a supersensitizing combination consisting of a spectral sensitizing dye and a non-light absorbing additive is the use of thiocyanate in the process of spectral sensitization as shown in U.S. Pat. No. 2.22L 805; No. 2,933,390 using bis-triazinylaminostilhene as shown in U.S. Pat.
37,089, using mercapto-substituted heterocyclic compounds as shown in U.S. Patent No. 3,457,078, and British Patent No. L 413,826. Iodide can be used as shown in the issue.

In addition, the method for adding the sensitizing dye to the photographic emulsion is as follows:
Various methods proposed in the past can be applied. For example, as described in U.S. Pat. No. 3,469,987, a sensitizing dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion. Good too. Still further, the sensitizing dyes of the present invention can be dissolved individually in the same or different solvents and the solutions can be mixed or added separately before being added to the emulsion.

In the present invention, when adding the sensitizing dye to the silver halide emulsion, examples of the dye solvent include methyl alcohol,
Water-miscible organic solvents such as ethyl alcohol and acetone are preferably used.

The sensitizing dye can also be used in combination with other sensitizing dyes or supersensitizers.

In addition to the above dyes, adsorbent photographic additives such as nitrogen-containing heterocyclic compounds can be used as the site indicator. General formulas of nitrogen-containing heterocyclic compounds include those shown in JP-A-81-205524, for example. Further, the dye and these additives can also be used in combination.

Even in such a case, in order to form the single-point seeded particles of the present invention, it is necessary that the dye and additives be added in an amount of 100%, preferably 150% or more of the saturated coverage.

The grain size of the silver halide used as the substrate may be fine grains of 0.1 micron or less, large grains with a projected area diameter of up to 10 microns, a monodisperse emulsion with a narrow distribution, or a polydisperse emulsion with a wide distribution. A dispersed emulsion may also be used.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Beaumontel (P.

Glafkides, Chimie et Physi
que Photographique Paul M
ontel, 1967), "Photographic Emulsion Chemistry" by Duffin, published by Focal Press (D, F.

Duffin, Photographic Emu
lsion Chemistry (Focal Pr.
ess, 1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al., published by Focal Press (V, L,
Zelikman et al., Making an
d Coating Photographic Emu
lsion, Focal Press + 196
It can be prepared using the method described in 4). That is, any of the acidic method, neutral method, ammonia method, etc. may be used, and the method for reacting the soluble silver salt with the soluble halogen salt may be any one-sided mixing method, simultaneous mixing method, or a combination thereof. good. A method in which particles are formed in an excess of silver ions (so-called back-mixing method)
You can also use As one form of the simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, a so-called Chondrald double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more types of silver halide emulsions formed separately may be mixed and used.

The silver halide emulsion consisting of the regular grains described above can be obtained by controlling I) Ag and pH during grain formation. For more information, please see Photographic Science.
and Engineering (Photographic
5Ciensand Engineerin
g) Volume 6, pages 159-165 (1962); Journal of Photographic Science (Jou
rnal of Photographic 5ci
ence) + 12 volumes.

pp. 242-251 (1964L U.S. Patent No. 3°6'55
, 394 and British Patent No. 1,413°748.

Further, tabular grains having an aspect ratio of 5 or more can also be used in the present invention. Tabular grains are described in ``Theory and Practice of Photography'' by C1eve, Photography
Theory and Practice (193
0) ), p. 131; Cutof, Photographic Science and Engineering
f, Photographic Science an
d Engineering) +Volume 14, 248~
257 pages (1970); U.S. Patent No. 4,434.22
No. 6, No. 4,414,310, No. 4゜433.048
No. 4,439.520 and British Patent No. 2,11
It can be easily prepared by the method described in No. 2.157. When tabular grains are used, there are advantages such as increased covering power and increased color sensitization efficiency by sensitizing dyes, and the above-cited US Pat. No. 4,434,226
It is detailed in the issue.

Silver halide solvents are useful to accelerate ripening. For example, it is known to have an excess of halogen ions present in the reactor to promote ripening. It is therefore clear that ripening can be accelerated simply by introducing a halide salt solution into the reactor. Other ripening agents can be used, and these ripening agents can be incorporated in their entirety into the dispersion medium in the reactor before the silver and halide salts are added, and one or more ripening agents can be used. can also be introduced into the reactor along with the addition of halide salts, silver salts or peptizers. As a further variant, the ripening agent can also be introduced independently at the halide salt and silver salt addition stages.

As ripening agents other than halogen ions, ammonia or amine compounds, thiocyanate salts such as alkali metal thiocyanate salts, especially sodium and potassium thiocyanate salts, and ammonium thiocyanate salts can be used. Special Publication No. 58-1410, Moisar et al., Journal of Photographic Science, Volume 25, 1977.19
As described on page 27, silver halide emulsions can be sensitized by internal reduction of grains during the precipitation formation process.

Chemical sensitization is described in James (T. H. James), The Photographic Process, 4th edition, Macmillan Publishing, 1977 (T. H. James).

The Theory of the Photographer
aphic Process, 4thed, Mac
millan, 1977), p. 67, 76, or as described in Research Disclosure, Vol. 120, April 1974
1-2008; Research Disclosure, Volume 34, June 1975, 13452, U.S. Patent No. 2,642
, No. 361, No. 3,297,446, No. 3,772.
No. 031, No. 3,857,711, No. 3.9OL 7
No. 14, No. 4,266.018, and No. 3,904
．． No. 415, as well as British Patent No. 1. 315. 755
pAg 5-10. At pH 5-8 and temperature 30-80°C, sulfur, selenium, chirulu,
This can be done using gold, platinum, palladium, iridium or a combination of these sensitizers. Chemical sensitization is optimally carried out in the presence of a gold compound and a thiocyanate compound and as described in U.S. Pat. No. 3,857,711, 4. 26
It is carried out in the presence of a sulfur-containing compound such as a sulfur-containing compound described in No. 6,018 and No. 4,054,457, or a sulfur-containing compound such as hypo, a thiourea compound, or a rhodanine compound. Chemical sensitization can also be carried out in the presence of chemical sensitization aids. The chemical sensitization aid used is a compound known to suppress fog and increase sensitivity during the chemical sensitization process, such as azaindene, azapyridazine, and azapyrimidine. Examples of chemical sensitization aid modifiers include U.S. Pat. No. 2,131,038, U.S. Pat.
No. and above-mentioned "Photographic Emulsion Chemistry" by Duffin, 138-1
It is described on page 43. In addition to or in place of chemical sensitization, U.S. Pat.
Reduction sensitization can be done, for example, using hydrogen, as described in US Pat. No. 984,249, and US Pat.
, No. 698, No. 2,743,182 and No. 2,74
3.183 using stannous chloride, thiourea dioxide, polyamines and such reducing agents, or by low pAg (e.g. less than 5) and/or high pH (e.g. greater than 8) treatment. Can be reduced sensitized. Color sensitization can also be improved by chemical sensitization methods described in U.S. Pat. Nos. 3,917,485 and 3,966,476.

Furthermore, the chemical sensitization method described in Japanese Patent Application No. 59-213957 is particularly effective when combined with the emulsion of the present invention.

The various additives described above are used in the photosensitive material related to the present technology, but various other additives can also be used depending on the purpose.

These additives are described in more detail in Research Disclosure Item 17643 (December 1978).
) and Item 18716 (1979, 1
(January), and the relevant sections are summarized in the table below.

1 Chemical sensitizer page 23 Page 648 right column 2 Sensitivity enhancer Same as above 3 Spectral sensitizer,
Pages 23-24 Page 648 Right column ~ Super sensitizer
Page 649 Right Column 4 Brightening Agent Page 24 5 Antifogging Agent Page 24-25 Page 649 Right Column and Stabilizer 6 Light Absorber, Fu Page 25-26 649 Right Column - Ilter Dyes 650 Left Column Ultraviolet Absorber 7 Stin Inhibitor page 25 right @ page 650 left to right column 8
Dye image stabilizer page 25 9 Hardener page 26 page 651 left column 10
Binder page 26 Same as above 11 Plasticizer, lubricant Page 27 650 Right column 12 Coating aid, surface Pages 26-27 Same as above Activator 13 Static inhibitor Page 27 Same as above As substrate particles when forming bonded particles, - It is more effective in providing electron concentration sites for particles that generally have a structure inside the particle and have high internal sensitivity when immature, such as double structure particles, multilayer structure particles, or twinned particles. it is conceivable that. However, any cubic, octahedral, tetradecahedral, or other polyhedral grains having higher-order surfaces made of normal crystals may be used. Also, mixtures of particles of various crystal forms may be used. In addition, its halogen composition is silver bromide, silver iodobromide,
Any silver halide crystal having a rock salt structure such as silver chloride, silver chlorobromide, silver chloroiodobromide, etc. may be used, but silver bromide or silver iodobromide is preferable, and more preferably silver halide. , the amount of deterioration contained is 5% or more of the total halogen4
More preferably, it is less than 0%. Further, the halogen composition of the epitaxially grown portion may be any mixed crystal consisting of silver bromide, silver chloride, silver iodide, or various combinations thereof, like the host, but it is preferably higher than the halogen composition of the silver halide grains of the substrate. It is more preferable to use a halogen composition that absorbs light only up to short wavelengths.

The amount of silver at the epitaxial growth site in the bonded grain is preferably from 0.5 to 50 mol% relative to the amount of silver halide in the substrate, more preferably at most 30 mol%, particularly preferably at most 10 mol%. , There is no particular restriction on the silver ion concentration when growing the epitaxial part, but if the main plane of the substrate grain is (11
1) If formed by a plane, p, Ag is 7.6
Under conditions lower than 0, bonds are likely to be formed in the plane or on the sides of the substrate particles (which may not be preferable when forming one bonding site per particle. In this case, p
Growth at Ag8°0 or higher is preferred.

The emulsion of the present invention can further bring out its characteristics by undergoing chemical sensitization.

Chemical sensitization may be performed before or after adding the site-indicating agent, or before, after, or during epitaxial growth. Furthermore, it may be before or after.

However, depending on the timing of chemical sensitization, it may become not only a surface latent image type emulsion but also an internal latent image type emulsion.

Even when the spectral sensitizer and site indicator are common, the spectral sensitizer can be further added after the water washing step.

As shown in JP-A No. 55-161229, in the bonded particles of the present invention, water-soluble metal salts such as Ir, Pb, and Cd are added at the time of epitaxial formation to form bonded portions. Electron trapping properties (etc.) can be imparted to the epitaxial growth site.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which include 3-methyl-4-amino-N, N-diethylaniline, 3- Methyl-4-amino-N-ethyl-N
-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-ethyl-N
-β-methoxyethylaniline and their sulfates, hydrochlorides, p-toluenesulfonates, and the like. Two or more of these compounds can be used in combination depending on the purpose.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, bromide salts, iodide salts,
Development inhibitors or anticapri agents such as benzimidazoles, benzothiazoles or mercapto compounds are generally included. In addition, as necessary, various types of compounds such as hydroxylamine, diethylhydroxylamine, sulfite hydrazines, phenyl semicarbazides, triethanolamine, catechol sulfonic acids, and triethylenediamine (1,4-diazabicyclo[2°2.2 cooctane)] may be added. preservatives, organic solvents such as ethylene glycol, diethylene glycol, development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, fogging agents such as sodium poron hydride; Auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids, such as ethylenediaminetetra Acetic acid, nitrilotriacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyliminodiacetic acid, 1-hydroxyethyl, dene-1,1-diphosphonic acid, nitrilo-N,N,N-)rimethylenephosphonic acid, ethylenediamine -N, N.

Representative examples include N',N'-tetramethylenephosphonic acid, ethylene glycol (0-hydroxyphenylacetic acid), and salts thereof.

Further, when performing reversal processing, black and white development is usually performed and then color development is performed. This black and white developer contains known black and white developing agents such as dihydroxyhenzenes such as hydroquinone, 3-pyrazolidones such as 1-phenyl-3-pyrazolidone, or aminophenols such as N-methyl-p-aminophenol. They can be used alone or in combination.

The pH of these color developing solutions and black and white developing solutions is generally 9 to 12. The amount of replenishment of these developing solutions depends on the color photographic material to be processed, but in general, the amount of replenishment of these developing solutions is 3! By reducing the bromide ion concentration in the replenisher,
rnI! , can also be: When reducing the amount of replenishment, it is preferable to prevent evaporation of the liquid and air oxidation by reducing the area of contact with the air in the processing tank.

Furthermore, the amount of replenishment can be reduced by using means for suppressing the accumulation of bromide ions in the developer.

The time for color development processing is usually set between 2 and 5 minutes, but the processing time can be further shortened by using high temperature, high pH, and high concentration of color developing agent.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be carried out simultaneously with the fixing process (bleach-fixing process) or separately. Furthermore, in order to speed up the processing, a processing method may be used in which bleaching is followed by bleach-fixing. Furthermore, treatment with two consecutive bleach-fixing baths, fixing treatment before bleach-fixing treatment, or bleaching treatment after bleach-fixing treatment can be carried out as desired depending on the purpose. Examples of bleaching agents include iron (■) and cobalt (■).
, compounds of polyvalent metals such as chromium (■), copper (II),
Peracids, quinones, nitro compounds, etc. are used.

Typical bleaching agents include ferricyanide 1 dichromate; organic complex salts of iron (]II) or cobalt (I[[), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, methyliminodiacetic acid, Aminopolycarboxylic acids such as 3-diaminopropanetetraacetic acid, glycol ether diaminetetraacetic acid, or complex salts of citric acid, tartaric acid, malic acid, etc.;
Persulfates; bromates; permanganates; nitrohenzenes, etc. can be used. Among these, aminopolycarboxylic acid iron (I [[) complex salts and persulfates, including ethylenediaminetetraacetic acid iron (In) complex salts, are preferred from the viewpoint of rapid processing and prevention of environmental pollution. Furthermore, aminopolycarboxylic acid iron(III) complexes are particularly useful in both bleach and bleach-fix solutions.

1) H of the bleaching solution or bleach-fixing solution using these aminopolycarboxylic acid iron ('III) complex salts is usually 5.5 to 8, but in order to speed up the processing, it is processed at a lower pH. You can also do that.

A bleach accelerator may be used in the bleaching solution, bleach-fixing solution, and their prebaths, if necessary.

Specific examples of useful bleach accelerators are described in U.S. Pat. No. 3,893,858, German Pat.
．． No. 290,812, No. 2,059゜988, JP-A No. 53-32,736, No. 53-57,831, No. 5
No. 3-37,418, No. 53-72,623, No. 53
-95,630, 53-95,631, 53-
104.232, 53-124', 424, 5
3-141.623, 53-28,426, Research Disclosure Floor No. 17,129 (1978
Compounds having a mercapto group or disulfide group as described in JP-A-50-140.129; Japanese Patent Publication No. 45-8,506;
Thiourea derivatives described in JP-A-52-20,832, JP-A-53-32,735, and US Pat. No. 3,706,561; West German Patent No. 1,127,715, JP-A-58-
Iodide salts described in West German Patent No. 16゜235 1 Polyoxyethylene compounds described in West German Patent No. 966゜410 and West German Patent No. 2,748.430; Polyamine compounds described in Japanese Patent Publication No. 45-8836 No. 49-42.434, No. 4!159,644, No. 53-94,927, No. 5
4-35.7.27, 55-26.506, 5
Compounds described in No. 8-163,940; bromide ions, etc. can be used.

Among them, compounds having a mercapto group or a disulfide group are preferable from the viewpoint of a large promoting effect, and are particularly preferred in U.S. Pat. No. 3,893,858 and Western Patent No. 1,290,812.
The compounds described in JP-A-53-95,630 are preferred. Also preferred are the compounds described in US Pat. No. 4,552,834. These bleach accelerators may be added to the photosensitive material. These bleach accelerators are particularly effective when bleach-fixing color light-sensitive materials for photography.

Examples of fixing agents include thiosulfates, thiocyanates, thioether compounds, thioureas, and large amounts of iodide salts, but thiosulfates are commonly used, with ammonium thiosulfate being the most widely used. Can be used for As the preservative for the bleach-fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

The silver halide color photographic light-sensitive material of the present invention is generally subjected to water washing and/or stabilization steps after desilvering treatment.

The amount of water used in the washing process depends on the characteristics of the photosensitive material (for example, depending on the materials used such as couplers), the application, the temperature of the washing water, the number of washing tanks (number of stages), the replenishment method such as countercurrent or forward flow, and various other conditions. Can be set over a wide range. Among these, the relationship between the number of washing tanks and the amount of water in the multistage countercurrent method is
urna 1 of the 5ociety of M
tion Picture and Televis
ion Engineers Volume 64, P, 24B-
253 (May 1955 issue).

According to the multi-stage countercurrent method described in the above-mentioned literature, the amount of water used for washing can be significantly reduced, but due to the increase in the residence time of water in the tank, bacteria will breed, and the generated suspended matter will adhere to the photosensitive material. The problem arises. In the processing of the color photosensitive material of the present invention, as a solution to such problems,
The method for reducing calcium ions and magnesium ions described in Japanese Patent Application No. 61-131.632 can be used very effectively. Also, JP-A-57-8,542
Chlorinated disinfectants such as isothiazolone compounds, cyabendazole, chlorinated sodium isocyanurate, and other benzotriazoles listed in the issue, "Chemistry of antibacterial and fungicidal agents" by Hiroshi Horiguchi, Sanitary technology complete volume "Sterilization of microorganisms" It is also possible to use the disinfectants described in "Encyclopedia of Antibacterial and Antifungal Agents" edited by the Japanese Society of Antibacterial and Antifungal Agents.

The pH of the washing water in the processing of the photosensitive material of the present invention is 4-
9, preferably 5-8. The washing water temperature and washing time can also be set variously depending on the characteristics of the photosensitive material, its use, etc., but generally it is 20 seconds to 10 minutes at 15-45°C, preferably 20 minutes.
A range of 30 seconds to 5 minutes at 5-40°C is selected. Furthermore,
The light-sensitive material of the present invention can also be directly processed with a stabilizing solution instead of washing with water. In such stabilization treatment, Japanese Patent Application Laid-Open No. 57-8,543, 58-14゜83
All known methods described in No. 4, No. 60-220,345 can be used.

Further, following the water washing treatment, a further stabilization treatment may be carried out, such as a stabilizing bath containing formalin and a surfactant, which is used as a final bath for color photosensitive materials for photography. .

Various chelating agents and antifungal agents can also be added to this stabilizing bath.

The overflow liquid resulting from the water washing and/or replenishment of the stabilizing liquid can also be reused in processes such as the desilvering process.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. In order to incorporate the color developing agent, it is preferable to use various precursors of the color developing agent. For example, U.S. Patent No. 3,342,59
Indoaniline compounds described in No. 7, No. 3,342.
No. 599, Research Disclosure 14,850
Schiff base-type compounds described in No. 15,159 and aldol compounds described in No. 13.924, U.S. Patent No. 3
, 719,492, JP-A-53-1
Examples include urethane compounds described in No. 35,628.

The silver halide color light-sensitive material of the present invention may optionally contain various 1-phenyl-3
- Pyrazolidones may be incorporated. Typical compounds are disclosed in JP-A-56-64,339 and JP-A-57-144,547.
No. 58-115.438, etc.

Various treatment liquids in the present invention are used at 10°C to 50°C. Normally, the standard temperature is 33°C to 38°C, but higher temperatures can be used to accelerate processing and shorten processing time, or lower temperatures can be used to improve image quality and stability of the processing solution. be able to. In addition, because of the nodal line of the photosensitive material, West German Patent No. 2.226,770 or U.S. Patent No. 3
, 674.499 may be carried out using cobalt intensification or hydrogen peroxide intensification.

Example 1 An emulsion in which double-structure twinned grains having an average equivalent sphere diameter of 1.6 μm and a core-shell ratio of 1=2 and an average iodine content of 10 mol % were dispersed at 0.8 mol per 1 kg of emulsion was used as a substrate emulsion. Using.

1000 cc of water was added to 850 g of this emulsion. Next, the water-added emulsion was heated to 45° and dissolved.

Furthermore, a spectral sensitizing dye for panchromatic color shown below was added to this emulsion.

The following four levels of the amount of pigment added were set with respect to the amount of saturated coverage.

1 0% 2 60% 3 200% Dye Addition Acid Halogen and silver were added in fixed amounts in the following combination to form bonded particles.

D (No addition = 31- The emulsion after epitaxial growth was treated with the usual desalting and dispersion process. The particles thus produced were prepared as samples by the replica method, and then observed with a transmission electron microscope to determine the epitaxial growth. The situation was investigated. Table 1 shows the percentage of grains containing substantially only one bonding site per grain contained in each emulsion.

1 in emulsion 4-A, which is one of the representative examples of the present invention.
Table 2 shows the distribution of the number of bonding sites per grain, and FIG. 2 shows electron micrographs of emulsions 1-A, 3-B, and 3-C of the present invention, emulsion 2-A of comparative example, and substrate grains. In the one-point inspection type particle of the present invention, the area of the joint part is 10% of the projected area of the substrate particle.
It is clear that:

Table 1 Example 2 Among the emulsions prepared in Example 1, the following emulsions were optimally chemically ripened using sodium thiosulfate at a exposure time of 1/100" second.

Table 3 The emulsion and protective layer were coated on a triacetylcellulose film support provided with an undercoat layer in the coating amounts shown in Table 4.

Table 4 (1) Emulsion layer 0 emulsion... Emulsion-1 to 8 shown in Table 1 (silver 1.7
0-2 mol/M) 0 coupler (1,5X10-” mol/a) 2H5 0 tricresyl phosphate (1,10 g/rr?) 0 gelatin (2,30 g/a) (2)
Protective layer 02.4-'; chlorotriazine-6-hydroxy-3
- Triazine sodium salt (0.08 g/proof) 0 Gelatin (1.80 g/I) After leaving these samples at 40'C and 70% relative humidity for 14 hours, they were exposed to light for sensitometry, The following color development process was performed.

The concentration of the treated sample was measured using a green filter.

The photographic performance results obtained are shown in Table 8.

The development process used here was carried out at 38°C under the following conditions.

1. Color development 2 minutes 45 seconds 2. Bleaching 6
Minute 30 seconds 3, wash with water・・・・・・・・・・・・・・・
3 minutes 15 seconds 4, established...
・6 minutes 30 seconds 5, wash with water・・・・・・・・・・・・
...3 minutes 15 seconds 6, stable...
...3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide
1.4g hydroxylamine sulfate m
Add 2.4g 4-(N-ethyl-N-βhydroxyethylamino)-2-methyl-aniline sulfate 4.5g water 1! Bleach solution Ammonium bromide 1'60.0g Aqueous ammonia (28%) '25.0mn Ethylenediamine-tetraacetic acid sodium salt 13'Og Glacial acetic acid 14m! add water
11 Fixer Sodium tetrapolyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) '175.0mI! .

Add 4.6 g of sodium bisulfite water 11 Add 8.0 ml of stabilized formalin water II! .

Conventional wedge exposure was performed at 1/100 seconds and 1/10000 seconds. The light source used was one whose color temperature was adjusted to 4800° using a filter, and a blue light was extracted and used using a blue filter. Sensitivity was compared based on fog and optical density of 0.2. The sensitivity is expressed as the sensitivity of the sample using emulsion 1-D as 100.
Table 5 shows the relative sensitivity as follows. It can be seen that the emulsion of the present invention has particularly high sensitivity at high illuminance compared to those having multiple junctions or those to which only dye is added. Furthermore, among the samples using Emulsions 3-A, 3-B, and 3-C of the present invention, Emulsion 3-A has the highest sensitivity because the light absorption threshold of silver halide in the epitaxial growth area is the shortest. It is clear that this shows that

Table 5 Example 3 The emulsion of the present invention prepared in Example 1 was optimally chemically sensitized using sodium thiosulfate and chloroauric acid, and coated samples were prepared in the same manner as in Example 2, and sensitometry was performed. However, as in Example 2, it was confirmed that the sample coated with the emulsion of the present invention exhibited high sensitivity, especially at high illuminance.

Example 4 A green-sensitive layer emulsion and a red-sensitive layer emulsion were prepared according to the method for preparing emulsion 3-B in Example 1. The spectral sensitizing dye used in Example 1 was used as it was in the emulsion for the red-sensitive layer. The spectral sensitizing dye shown below was used in the green sensitive layer.

These emulsions are Emulsion 4, which has undergone conventional gold-sulfur sensitization.
, 5. Sample 101 is a multilayer color photosensitive material consisting of each layer having the composition shown below on a cellulose triacetate film support which is undercoated with these emulsions.
It was created.

(Composition of photosensitive layer) The coating amount is the amount expressed in g/rd unit of silver for silver halide, colloidal silver and coupler, and the number of moles per mole of silver halide in the same layer for sensitizing dye. It was shown in

1st layer: antihalation layer black colloidal silver Silver coating amount 0.2 gelatin
2.2UV-10,1 UV-20,2 Cpd-10,05 Solv-10,01 Solv-20,01 Solv-30,08 Second layer: Intermediate layer. Red-sensitive layer and green-sensitive layer emulsions prepared in this way Fine-grain silver bromide (equivalent sphere diameter 0.07μ) ExC-20,009 ExC-30,023 ExC-60,14 4th layer: Second red-sensitive emulsion layer Odor Silveride emulsion (Ag1 16 mol%, internal high AgI type 2
Equivalent sphere diameter 1.0 μm Coefficient of variation of equivalent sphere diameter 25%, plate-shaped particles, diameter/thickness ratio 4° Silver coating amount 0.55 Gelatin 0.7ExS-1
3xlO-'ExS-21XIO-'ExS-30,3X10-'ExS-,40,3X10-' ExC-60.08 ExC-30,05 ExC-40,10 Coefficient of variation of equivalent sphere diameter 14%, tetradecahedral particle ) Silver coating amount
0.2 Silver iodobromide emulsion (Ag1 4.0 mol%, internal high AgI type 9 sphere equivalent diameter 0.4μ2 sphere equivalent diameter coefficient of variation 22%, 14
Face piece particles) Silver coating amount 0.1 Gelatin 1.2ExS-
55xto-' F, xS-62X10-'ExS-71XIO-' ExM-10,41 ExM-20,10 ExM-50,03 Solv-10,2 8th N: Second green-sensitive emulsion layer Silver iodobromide emulsion ( Ag1 10 mol%, internal high iodine type 9
Equivalent sphere diameter 1.0μ1 Coefficient of variation of equivalent sphere diameter 25%, plate-like ExS-70,8X10-' ExM-40,04 ExM-30,01 ExC-40,005 Solv-1' 0.2
11th layer: Yellow filter layer Cpd-30,05 Gelatin 0. 5Solv
-10,1 12th layer: Intermediate layer gelatin 0.5Cpd-2
0,1 13th layer: 1st blue-sensitive emulsion layer Silver iodobromide emulsion (Ag1 10 mol%, internal high iodine type 1
Equivalent sphere diameter 0.7 μ2 Coefficient of variation of equivalent sphere diameter 14%, tetradecahedral grains) Silver coating amount 0.1 Silver iodobromide emulsion (AgI 4.0 mol%, inner grain silver iodobromide (AgI '2 mol) %, average type.

Equivalent sphere diameter 0.13μ) Silver coating amount 0.2 Gelatin 0.36
lo-) 16th layer: 3rd blue-sensitive emulsion layer silver iodobromide emulsion (Ag1 14.0 mol%, internal high Agl
Mold, equivalent sphere diameter 1.5 μ9 Coefficient of variation of equivalent sphere diameter 28%, plate-shaped particles, diameter/thickness ratio 5° Silver coating amount 1.0 Gelatin 0. 5ExS-
81,5x1o-' ExY-10,2 Solv-10,07 17th layer: 1st protective layer gelatin 1.8UV-1 (
1,l UV-20,2 Solv-10,01 Solv-20,01 V-1 1,1 COCOOCH3 ■ x/y=7/3 (weight ratio) UV-2 ExM-3 (n Shi2 ExC-4 o (n)C,zH2sxC-5 I2H2S xM-1 CH.

xY-I xY-2 xS-1 xS-6 2H5 ■ xS-8 (CH2) 4 SO3 days (CHI) 4 SOs
H-N (C2H5)xS-7 So 1v-13o Iv-2 olv-3 olv-4 pa-1 pd-3

[Brief explanation of the drawing]

FIG. 1 is a schematic representation of single-point seeded particles according to the present invention. vl in (a) and (b) represents an epitaxial growth part. ■1 and v in (C,)
2 are epitaxial growth parts, 1 is a main growth part, and 2 is a micro growth part. Figure 2 shows the substrate grains and emulsion (2-A) in Example-1.
), (3-A), (3-B), and (3-C) are electron micrographs showing the crystal structure of silver halide grains in (3-C), and the magnification is 3,000 times. Patent Applicant: Fuji Photo Film Co., Ltd. Figure 1 Date of Date: 1986

Claims (1)

[Claims] In a silver halide photographic emulsion comprising silver halide grains dispersed in a binder, 30% or more of the projected area of all silver halide grains is composed of bonded silver halide grains, and the bonded grains are grains 1 1. A silver halide photographic emulsion, which has substantially one bonding part per contact, and the crystal structure of the substrate grains is a rock salt structure.